CN100515938C - Method for separating and extracting carbon nano tube from carbon nano tube-concentrated acid reaction solution - Google Patents
Method for separating and extracting carbon nano tube from carbon nano tube-concentrated acid reaction solution Download PDFInfo
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- CN100515938C CN100515938C CNB2007100519526A CN200710051952A CN100515938C CN 100515938 C CN100515938 C CN 100515938C CN B2007100519526 A CNB2007100519526 A CN B2007100519526A CN 200710051952 A CN200710051952 A CN 200710051952A CN 100515938 C CN100515938 C CN 100515938C
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- concentrated acid
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Abstract
The present invention provides a method of separating and extracting carbon nanotubes from carbon nanotube-concentrated acid reaction solution, which comprises the steps of: executing face finish of the carbon nanotube in the carbon nanotubes-concentrated acid reaction solution by the reaction between the functional group, comprising hydroxide radical and carboxyl, of the surface of the carbon nanotube and surface active agent siloxane radical, so that the carbon nanotube forms micelle and aggregates; separating the carbon nanotube derivates from the solution by using the general separation method; obtaining pure carbon nanotube through thermal weight loss treatment; wherein the obtained carbon nanotube derivates can carry out further functionalized reaction. The present invention can prevent the separation device and the filtering device from being corrupted by concentrated acid, be adapted to separate carbon nanotubes from carbon nanotube-concentrated acid reaction solution with different concentrations, and improve the separating and extracting efficiency. The whole process is simple and high efficiency.
Description
Technical field
The present invention relates to field of carbon nanotubes, particularly relate to a kind of method by separation and Extraction carbon nanotube in carbon nanotube-concentrated acid reaction solution.
Background technology
Because the potential use of carbon nanotube causes the very big concern of international chemistry, physics, material educational circles, people widen its Application Areas in all its bearings.Nitration mixture refluxes or supersound process is the basis and one of routine, effective means of functionalization.But, the green sub of reaction product from efficient purification be the bottleneck of current techniques.Carbon nanotube is after the concentrated acid oxidation, cutting short, and a large amount of hydroxyls and carboxyl are contained in the surface, forms homogeneous, stable solution with concentrated acid, filters, ordinary method such as centrifugal, chromatographic separation is used for carbon nanotube and concentrated acid liquid phase separation efficient is not high.And this solution is big to separating device corrodibility, the harm environment.
In a word, Nano-technology Development has had considerable technique means and has solved carbon nanotube purification problem so far, still, separates the highly effective method foundation as yet of purification carbon nanotube from homogeneous carbon nanotube and concentrated acid reaction solution.Therefore, the isolation technique of carbon nanotube-concentrated acid reaction solution still has improved space.And the carbon nano tube derivative of generation has good processing properties and further functionalization prospect, has purposes widely at aspects such as carbon nanotube-polymer composite, bio-identification and sensings.
Summary of the invention
Technical problem to be solved by this invention is: provide a kind of method by separation and Extraction carbon nanotube in carbon nanotube-concentrated acid reaction solution that meets the environmental protection theory, to overcome the defective that prior art exists.
The technical scheme that the present invention solves its technical problem employing is: utilize carbon nano tube surface to contain the functional group and the C of hydroxyl, carboxyl earlier
12～C
50Siloxanes reaction on the silicone surfactant, carbon nanotube in carbon nanotube-concentrated acid reaction solution is carried out finishing, make in the solution carbon nanotube form micella and assemble, adopt conventional isolating method from solution, to isolate carbon nano tube derivative again, handle through thermal weight loss then, can obtain purified carbon nanotube; The carbon nano tube derivative that obtains also can carry out further reaction kinetic.
The present invention compared with prior art, the advantage that has mainly is: avoided the corrosion of concentrated acid to separation, filtration unit, be applicable to the separation of the carbon nanotube-concentrated acid reaction solution of various concentration, and greatly improved separation and Extraction efficient, whole separation and Extraction carbon nanotube process operation is simple, environmental protection, highly effective, thereby for the separation of carbon nanotube, extraction and further reaction kinetic and application are laid a good foundation.
Description of drawings
Fig. 1 is a nanotube derivative synoptic diagram.Wherein: A is the synoptic diagram of carbon nano tube derivative; B is the synoptic diagram of the further reaction kinetic product of embodiment 7 carbon nano tube derivatives (having the double ion organic layer, ionic bilayer coating).
Fig. 2 is projection electron microscope (TEM) collection of illustrative plates of the further reaction kinetic product of embodiment 7 multi-walled carbon nano-tubes derivatives.This product has ion organic layer (ionic bilayer coating).
Fig. 3 is the infrared spectra of embodiment 1 multi-walled carbon nano-tubes derivative.Wherein: A is the infrared spectra of multi-walled carbon nano-tubes raw material; B is the infrared spectra of multi-walled carbon nano-tubes behind the concentrated acid ultrasonic reaction; C is the infrared spectra of multi-walled carbon nano-tubes derivative.
Embodiment
The invention provides a kind of method by separation and Extraction carbon nanotube in carbon nanotube-concentrated acid reaction solution, that is: utilize carbon nano tube surface to contain hydroxyl earlier, the functional group of carboxyl and the reaction of tensio-active agent siloxanes, carbon nanotube in carbon nanotube-concentrated acid reaction solution is carried out finishing, make in the solution carbon nanotube form micella and assemble, adopt conventional isolating method from solution, to isolate carbon nano tube derivative again, handle through thermal weight loss then, can obtain purified carbon nanotube, the carbon nano tube derivative that obtains also can carry out further reaction kinetic, to enlarge its range of application.
The step of aforesaid method comprises: provide a kind of carbon nanotube-concentrated acid to reflux or ultrasonic reaction solution; Adding silicone surfactant and carbon nanotube wherein carry out surface reaction in the solution, it is produced assemble; Utilizing centrifuging, dialysis method and filtration method to carry out routine above-mentioned reacted carbon nanotube-concentrated acid reaction solution separates; Carbon nano tube derivative carries out the thermal weight loss processing or carries out further reaction kinetic.Concrete steps are as follows:
(1) getting carbon nanotube-concentrated acid and reflux or ultrasonic reaction solution, is silicone surfactant-methanol solution of 1: 0.2 to wherein adding volume ratio, and the massfraction of this solution is 40%.Described carbon nanotube-concentrated acid reaction solution comprises concentrated acid and carbon nanotube reacted solution; Concentrated acid is the solution that comprises sulfuric acid, the various blending ratios of nitric acid.Described silicone surfactant is for containing siloxanes long-chain tensio-active agent, and its molecular chain length is C
12～C
50
The explanation of this step: carbon nanotube refluxes with concentrated acid usually or ultransonic method is purified, cut short and surface hydroxyl and carboxylated.Utilize chemical reaction such as concentrated acid oxidation style to make some groups in the carbon nanotube grafting, as-COOH (hydroxyl) ,-OH (hydroxyl), at this moment, carbon nanotube will show the polarity similar to such group, dissolves in the solvent close or identical with such group polarity.Hydroxyl that obtains and carboxylic carbon nano-tube can form the nano-dispersed state in acid solution, going through the several months can sedimentation yet.
(2) stir 0.4～0.6 hour under the room temperature, can make carbon nano tube surface functional group and tensio-active agent siloxanes sufficient reacting, produce and assemble, the carbon nanotube micella of state of aggregation promptly in reacted solution, occurs being.
(3) separate by conventional separation method, through ethanol and washing, obtain carbon nano tube derivative again.Conventional separation method comprises filtration method, dialysis method and centrifuging.
Add and to have the carbon nanotube micella soon behind the tensio-active agent and occur, get that its reacted solution is filtered, dialysis or centrifugation can obtain carbon nanotube.The carbon nanotube that obtains common solvent such as crude product water and the ethanol washing of deriving just obtains purer carbon nano tube derivative.
(4) carbon nano tube derivative is made further reaction kinetic or thermal weight loss and handled, can obtain purified carbon nanotube.Resulting carbon nanotube can be multi-walled carbon nano-tubes or Single Walled Carbon Nanotube.
Above-mentioned thermal weight loss is handled and can be carried out under nitrogen or argon shield, and temperature is 500～800 ℃.
The invention will be further described below in conjunction with specific embodiment, but do not limit the present invention.
Embodiment 1: by separation and Extraction multi-walled carbon nano-tubes in multi-walled carbon nano-tubes-concentrated acid reaction solution
At first, get an amount of multi-walled carbon nano-tubes-concentrated acid reaction solution, concentrated acid is the sulfuric acid of arbitrary volume ratio, the solution of nitric acid blending ratio; In described reaction soln, add volume ratio again and be silicone surfactant-methanol solution (massfraction 40%) of 1: 0.2, stir 0.5h under the room temperature; Treat to occur in the solution that micella can be dialysed, filtration or centrifugation, the product that obtains obtains comparatively purified carbon nano tube derivative through ethanol and washing.This carbon nano tube derivative can carry out thermal weight loss under the protection of nitrogen-argon gas and 700 ℃ handles, and can obtain purified multi-walled carbon nano-tubes; Or carry out further reaction kinetic.
Embodiment 2: by separation and Extraction multi-walled carbon nano-tubes in the multi-walled carbon nano-tubes concentrated acid reaction solution
Remove that churning time is 0.4h under the room temperature, and carry out under the protection of nitrogen-argon gas and 500 ℃ outside thermal weight loss handles, other is with embodiment 1.
Embodiment 3: by separation and Extraction multi-walled carbon nano-tubes in the multi-walled carbon nano-tubes concentrated acid reaction solution
Remove that churning time is 0.6h under the room temperature, and carry out under the protection of nitrogen-argon gas and 800 ℃ outside thermal weight loss handles, other is with embodiment 1.
Embodiment 4: by separation and Extraction Single Walled Carbon Nanotube in Single Walled Carbon Nanotube-concentrated acid reaction solution
At first, get an amount of Single Walled Carbon Nanotube-concentrated acid reaction solution, concentrated acid is the sulfuric acid of arbitrary volume ratio, the solution of nitric acid blending ratio; In described reaction soln, add volume ratio again and be silicone surfactant-methanol solution (massfraction 40%) of 1: 0.2, stir 0.5h under the room temperature.Treat to occur in the solution that micella can be dialysed, filtration or centrifugation, the product that obtains obtains comparatively purified carbon nano tube derivative through ethanol and washing.This carbon nano tube derivative can carry out thermal weight loss under the protection of nitrogen-argon gas and 700 ℃ handles, and can obtain purified Single Walled Carbon Nanotube; Or carry out further reaction kinetic.
Embodiment 5: by separation and Extraction Single Walled Carbon Nanotube in the Single Walled Carbon Nanotube concentrated acid reaction solution
Remove that churning time is 0.6h under the room temperature, and carry out under the protection of nitrogen-argon gas and 800 ℃ outside thermal weight loss handles, other is with embodiment 4.
Embodiment 6: by separation and Extraction Single Walled Carbon Nanotube in the Single Walled Carbon Nanotube concentrated acid reaction solution
Remove that churning time is 0.4h under the room temperature, and carry out under the protection of nitrogen-argon gas and 500 ℃ outside thermal weight loss handles, other is with embodiment 4.
Embodiment 7: carry out further reaction kinetic by the multi-walled carbon nano-tubes derivative
Take by weighing above-mentioned multi-walled carbon nano-tubes derivative 3g and 20mL sulfonate (C
9H
19C
6H
4O (CH
2CH
2O)
10SO
3 -K
+, the 16.5wt./vol.% methanol solution) and at 70 ℃ of following stirring reaction 24h, mixture water that obtains and methanol wash 3～6 times and 70 ℃ of dryings 2 days, promptly obtain having the double ion organic layer derivative of (ionic bilayer coating).
Claims (6)
1. the method by separation and Extraction carbon nanotube in carbon nanotube-concentrated acid reaction solution is characterized in that: utilize carbon nano tube surface to contain the functional group and the C of hydroxyl, carboxyl earlier
12～C
50Siloxanes reaction on the silicone surfactant, carbon nanotube in carbon nanotube-concentrated acid reaction solution is carried out finishing, make in the solution carbon nanotube form micella and assemble, obtain carbon nano tube derivative by filtration, dialysis or centrifugal treating again, then, carbon nano tube derivative carries out thermal weight loss under 500～800 ℃ of temperature handles, and obtains purified carbon nanotube.
" tensio-active agent " in the claim 1 is limited to " C
12～C
50Tensio-active agent "; Involved " hydroxyl, carboxyl " is " hydroxyl and carboxyl "; According to auditor's suggestion, " tensio-active agent siloxanes " changed to " siloxanes on the silicone surfactant " simultaneously.
2. the method for extraction carbon nanotube according to claim 1 is characterized in that adopting following step:
(1) getting carbon nanotube-concentrated acid and reflux or ultrasonic reaction solution, is silicone surfactant-methanol solution of 1: 0.2 to wherein adding volume ratio, and the massfraction of this solution is 40%, and the molecular chain length of silicone surfactant is C
12～C
50,
(2) stir 0.4～0.6 hour under the room temperature, make the siloxanes sufficient reacting on carbon nano tube surface functional group and the silicone surfactant, produce dirt and assemble, the carbon nanotube micella of state of aggregation promptly in reacted solution, occurs being,
(3) by filtration, dialysis or centrifugal treating, through ethanol and washing, obtain carbon nano tube derivative again,
(4) carbon nano tube derivative is made thermal weight loss and handled, obtain purified carbon nanotube.
3. the method for extraction carbon nanotube according to claim 2 is characterized in that: described carbon nanotube-concentrated acid reaction solution comprises the solution behind concentrated acid and carbon nanotube backflow or the ultrasonic reaction; Concentrated acid is the solution that comprises sulfuric acid, the various blending ratios of nitric acid.
4. the method for extraction carbon nanotube according to claim 2 is characterized in that: described carbon nanotube is multi-walled carbon nano-tubes or Single Walled Carbon Nanotube.
5. the method for extraction carbon nanotube according to claim 2 is characterized in that: it is to carry out under nitrogen or argon shield that thermal weight loss is handled.
6. the method for extraction carbon nanotube according to claim 2 is characterized in that: carbon nano tube derivative also can carry out further reaction kinetic.
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| CNB2007100519526A CN100515938C (en) | 2007-04-24 | 2007-04-24 | Method for separating and extracting carbon nano tube from carbon nano tube-concentrated acid reaction solution |
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| CN102081990B (en) * | 2010-12-27 | 2012-05-30 | 河南城建学院 | High-dielectric composite material containing carbon nanotube fluids (CNTFs) |
| CN102331449B (en) * | 2011-06-10 | 2013-05-08 | 西南大学 | Electrochemical sensor and preparation method thereof |
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| 硅烷偶联剂对单璧碳纳米管的化学修饰. 苏小红等.化工新型材料，第35卷第3期. 2007 |
| 硅烷偶联剂对单璧碳纳米管的化学修饰. 苏小红等.化工新型材料，第35卷第3期. 2007 * |
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